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1.
A new alternating double aquo-bridged and single cyano-bridged polymeric complex {[Ba2(phen)4(H2O)6Fe(CN)6]·Cl·2(phen)·3H2O}n (1) (phen = 1,10-phenanthroline) has been synthesized and structurally characterized. In the crystal structure the two centrosymmetric [Ba2(phen)4(H2O)6] units are bridged through two trans CN groups of [Fe(CN)6]3− ion, which results in the formation of a zig-zag polymeric chain. In each [Ba2(phen)4(H2O)6] unit, the two Ba centers are joined by double aquo bridges. Both the Ba atoms are 9-coordinated with distorted mono-capped square antiprismatic geometry. An elaborate hydrogen bonding system holds the parallel polymeric chains together.  相似文献   

2.
A one-dimensional stair-like coordination polymer, [Fe2L2Na2(CH3CN)2(Et2O)2]n {1, where L4 = N,N’-bis-(2-mercaptophenyl)-2-methyl-2-[(2-methylthio)phenylmethyl] malonyl diamide}, was produced from the one-pot reaction of iron(III) chloride with 2-methyl-2-[(2-methylthio)phenylmethyl] malonyl chloride, 2-aminobenzenethiol and sodium hydride in DMF solution, and was structurally characterized. The dimeric pentacoordinate Fe(III) anionic units are linked by two bridging four-coordinate Na+ cations. Each trivalent iron atom is equatorially coordinated by two deprotonated carboxamido N and S atoms of the ligand. The bridging S atom, occupying the axial position, accomplishes the square-pyramidal geometry of iron center. The coordination environment is very similar to the unmodified active site of Fe-containing nitrile hydratase. In addition, the electronic and magnetic properties of this dimeric complex are included in this report.  相似文献   

3.
A novel supramolecular assembly consisting of sodium-dibenzo-18-crown-6(DB18C6) complex cation [Na(C20H24O6)(CH3CN)2]2+ and isopolyanion [Mo6O19]2− has been demonstrated in the 3D structure of [Na(C20H24O6)(CH3CN)2]2[Mo6O19] · 4CH3CN (1). Weak intermolecular forces (C–HO hydrogen bonds) between isopolyanion and crown ether play a significant role in the construction of supramolecular framework in the crystal structure of 1. Compound 1 has been characterized in the solid state by single crystal X-ray diffraction, IR, CHN analysis, and TGA.  相似文献   

4.
A novel polymeric cobalt(II) complex with flexible ligand, [Co(BTB)2(NCS)2]n 1 {BTB = 1,4-bis(1,2,4-triazol-1-yl)butane} has been prepared and structurally characterized by single-crystal X-ray diffraction as well as with elemental analysis, infrared spectroscopy and thermogravimetric analysis. The complex 1 consists of two discrete constituents, A and B, with the same chemical formula [Co(BTB)2(NCS)2] but different connecting mode. The six-co-ordination of Co2+ in A and B is in a distorted octahedral environment formed by four nitrogen atoms of the triazoles and two nitrogen atoms from two trans thiocyanato ligands. The structures of A and B demonstrate a one-dimensional neutral looped chain through two BTB-bridges and a two-dimensional network in which four BTB bridge four Co(II) atoms, respectively. A and B interpenetrate in an inclined fashion. The flexible BTB ligand exhibits three different configurations in 1.  相似文献   

5.
A classical ionic inorganic complex Na2[Cu(mnt)2] (mnt2− = maleonitriledithiolate = 1,2-dicyanoethylenedithiolate), that acts as a template in assembling neutral [Cu(salen)] (salen = bis(salicylidene)ethylenediamine) complexes forming a framework type arrangement, is accommodated in the channel formed in the crystal structure of a new type of host–guest compound [Cu(salen)]4 · Na2[Cu(mnt)2] (1). The non-covalent supramolecular interactions among [Cu(salen)] complexes and between [Cu(salen)] and [Cu(mnt)2]2− complexes in the crystal lattice of 1 result in weak antiferromagnetic coupling.  相似文献   

6.
A new compound, {[Cu2(DF)2H2O]2SiMo12O40} (1) (DF = 4,5-diazafluoren-9-one), has been hydrothermally synthesized and characterized by routine methods and single crystal X-ray diffraction. In 1, all the DF only adopt the unusual bidentate coordination mode for the first time coordinating to Cu atoms to form copper-dimers which link [SiMo12O40]4− clusters obtaining an intertwined double chain. Furthermore, the luminescent and electrochemical properties of the title compound have been studied.  相似文献   

7.
Reactions of CuCl2, K2[Ni(CN)4]/K3[Co(CN)6], and 5-amino-1H-tetrazole led to cyanide-bridged mixed-valence Cu(II/I) complexes, [Cu(H2O)3Cu3(CN)5] (1) and [Cu(H2O)4][Cu4(CN)6] (2).The uncommon semi-closed {Cu2(CN)3} dimmers in 1 are bridged by μ3-C,C,N cyanide ligands to afford rare 1D centipedal-like chain motifs, which are further bridged by μ2-C,N and metalloligand “CN–Cu(4)–CN” to finish sophisticated zeolite-like 3-D structure. Topologically, 1 is the first example of uninodal 7-connected sev-like cyanide-bridged network. Compound 2 consists of two-dimensional honeycomb-related anionic layers [Cu4(CN)6]2 , within which the [Cu(H2O)4]2 + cations are intercalated into alternate interlamellar space. Compound 1 shows antiferromagnetic couple arising from pure ground-state configuration of Cu(II) mediated by diamagnetic bridges –CN–CuI–CN −. The inclusion compound 2 shows blue photoluminescence originated from Cu(I) center to the unoccupied π* orbital of the cyanide ligand (MLCT) charge transfer.  相似文献   

8.
One new metal-organic polymer formulated as [Fe210-btc)0.52-ox)0.52-O)1.5]n 1 (btc = 1,2,4,5-benzenetetracarboxylate, pyramellitate; ox = oxalate) has been synthesized by low-temperature solid-state reaction and characterized by single-crystal X-ray diffraction, elemental analyses, TGA, IR spectra and UV–visible spectra. Complex 1 presents the first 3D coordination network structure constructed by bridging btc, ox and O mixed ligands. In 1, carboxyl groups of btc are all deprotonated and they have a new type of μ10-btc coordination mode. The third-order non-linear optical (NLO) properties of the title compound 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 5.98 × 10−30 esu for 1 in a 7.45 × 10−4 mol dm−3 DMF solution.  相似文献   

9.
A new dinuclear complex [Cu2(OAc)2(OH)(dpa)2] PF6 · H2O (1) is prepared and structurally and magneto-structurally characterized. The monocationic core contains one acetate in familiar bidentate η112-bridge and another in the rare monoatomic bridge along with one hydroxo intermediary. 1 packs through N–H…O and O–H…O hydrogen bonds and π…π interaction resulting a 3D supramolecular continuum and displays high-energy intraligand 1(π − π*) fluorescence and intraligand 3(π − π*) phosphorescence in glassy solution.  相似文献   

10.
The novel six-coordinated gadolinium(III) complex of formula [Gd2(dca)4(OH)2(NITpPy)4] (1) (dca = dicyanamide, NITpPy = 4-pyridyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-oxy-3-oxide) has been prepared and characterized by X-ray crystallography. Compound 1 is a dimer structure made up of double μ1,5-dca-bridged gadolinium(III) ions and one terminal dca ligand; variable-temperature magnetic susceptibility measurements reveal the occurrence of a significant ferromagnetic interaction directly spin polarization through the NITpPy–Gd(III)–NITpPy pathway with J = 11.56 cm−1.  相似文献   

11.
A novel iron(II) complex, trans-[FeL2(NCS)2][FeL2(CH3OH)2](NCS)2 (1) with 4-amino-3-(p-chlorophenyl)-5-(2-pyridyl)-1,2,4-triazole (L) has been successfully synthesized and characterized. X-ray crystallography analysis shows that 1 is the first example in the mononuclear triazole-based complexes consisting of two distinct molecules: trans-[FeL2(NCS)2] and trans-[FeL2(CH3OH)2](NCS)2 with each octahedral iron(II) center coordinated axial by two NCS ions in Fe1 but two MeOH molecules in Fe2. Moreover, 1 can lose two MeOH molecules at 220 °C to form trans-[FeL2(NCS)2] (2) which can be transformed to 1 when recrystallizing 2 in methanol. Both 1 and 2 are high-spin species in the range of 1.8–300 K.  相似文献   

12.
Attempts to prepare the [As(NtBu)3]3− trianion by the reaction of As(NMe2)3 with [tBuNHLi]n (1:3 monomer equiv.) proved unsuccessful. However, if the reaction is carried out with an excess of tBuNH2 (3 equiv.) the target complex [{As(NtBu)3}2Li6] (1) is obtained. This is the first example of a complex containing an [As(NR)3]3− trianion.  相似文献   

13.
Direct reaction of gold(I) chloride with 3-nitrobenzaldehyde thiosemicarbazone (3-NO2-Hbtsc) in the presence of triphenylphosphine in acetonitrile has yielded ionic complex, [Au2(3-NO2-Hbtsc)4]Cl2 · 2CH3CN (1). It exhibited an intense fluorescence band (λem) at 383 nm (λex = 300 nm), and two bands of medium intensity at 413 and 436 nm (λex = 350 nm). Complex 1 represents first example of ionic gold(I) complex with a thiosemicarbazone.  相似文献   

14.
The iron complex generated in situ from Fe(CF3SO3)2 and the new tridentate N ligand mpzbpy (mpzbpy stands for 6-(3,5-dimethylpyrazol-1-ylmethyl)-6′-methyl-2,2′-bipyridine) mediates the room temperature oxidation of cyclohexane to cyclohexanol and cyclohexanone, and the epoxidation of cyclooctene to cyclooctene oxide. X-ray diffraction studies of single crystals obtained by reaction of iron(II) triflate with mpzbpy in methanol in the presence of ascorbic acid reveals the formation of a dinuclear complex, namely [Fe2(mpzbpy)2(C2O4)(CF3SO3)2] (1), where two iron(II) ions are bridged by an oxalato dianion originating from the oxidative cleavage of ascorbic acid. Magnetic susceptibility measurements of 1 show that the two metallic centres are weakly antiferromagnetically coupled, with a J value of −1.74(1) cm−1.  相似文献   

15.
Reactions of [OsCl2(PPh3)3] 1 with the [NEt4]+ salts of the [6-Ph-nido-6-CB9H11] anion 2 and the [arachno-6-CB9H14] anion 3 each proceed selectively in methanol solution with the elimination of one boron-containing fragment from the starting cluster polyhedron, yielding together a short series of three novel 10-vertex hydridoosmamonocarbaboranes of isocloso {OsCB8} cluster geometry.  相似文献   

16.
The first example of disubstituted Lindqvist-type polyoxomolybdate {[V(2,2-bipy)2]2(4,4-bipy)[Te2Mo4O19]} has been synthesized hydrothermally and characterized by elemental analyses, XPS, IR, TG-DTA and X-ray single crystal diffraction. The structural analysis shows that the neutral molecular unit [V(2,2-bipy)2]2[Te2Mo4O19] consists of a novel Lindqvist-type polyanion [Te2Mo4O19]6− supporting two vanadyl moieties [V(2,2-bipy)2]3+, and such neutral molecules are joined together by π − π stacking interactions between the pyridine groups to form a two-dimensional grid-like network with non-coordinating “guest” 4,4-bipys encapsulated.  相似文献   

17.
Two cationic pentamethylcyclopentadienyl metal-based hexanuclear complexes with trigonal prismatic architecture have been synthesised through a two-step strategy. The dinuclear complexes [M(η5- C5Me5)(μ-Cl)Cl]2 (M = rhodium and iridium) react with 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) in dichloromethane to give the trinuclear complexes [Rh35-C5Me5)33-tpt)Cl6] (1) and [Ir35-C5Me5)33-tpt)Cl6] (2), respectively. Addition of silver triflate to 1 and 2 in dichloromethane connects two identical triangular panels to form the hexanuclear metallo-prismatic cations [Rh65-C5Me5)63-tpt)2(μ-Cl)6]6+ (3) and [Ir65-C5Me5)63-tpt)2(μ-Cl)6]6+ (4), respectively. Cations 3 and 4 have been isolated as their triflate salts and characterised by 1H NMR, IR and UV/visible spectroscopy.  相似文献   

18.
A facile [Ru(acac)2(CH3CN)2]PF6 (Hacac = acetylacetone) (1) catalyzed oxidation of alcohols to aldehydes or ketones using H5IO6 as oxidant in water at room temperature is described.  相似文献   

19.
An unusual copper(II) complex [Cu(L1a)2Cl2] CH3OH·H2O·H3O+Cl (1a) was isolated from a solution of a novel tricopper(II) complex [Cu3(HL1)Cl2]Cl3·2H2O (1) in methanol, where L1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H2L1) was synthesized and physico-chemically characterized, while the formation of the complex 1a was followed by time-dependant monitoring of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands corresponding to O → Cu(II) charge transfer.  相似文献   

20.
Hydrothermal reaction of CuCN, K3[Fe(CN)6] and 1,10-phenanthroline affords a novel cyanide-bridged copper(I) coordination polymer [Cu3(CN)3(phen)]n (1). The complex displays an interesting one-dimensional neutral double helical framework with (phen)Cu–CN– side-arms as interchain bridges. The double helical chains are close packed in a parallel fashion, and the phen ligands stack in an interpenetrating mode, which leads to π–π interactions between parallel phen planes. The thermal stability and fluorescent property have also been investigated.  相似文献   

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